CN101189276A - Toner - Google Patents
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- CN101189276A CN101189276A CNA2006800137737A CN200680013773A CN101189276A CN 101189276 A CN101189276 A CN 101189276A CN A2006800137737 A CNA2006800137737 A CN A2006800137737A CN 200680013773 A CN200680013773 A CN 200680013773A CN 101189276 A CN101189276 A CN 101189276A
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Abstract
A series of resins were synthesized using a range of bio-based materials to control the molecular architecture, and therefore the properties, of the inventive resins. The resins were formulated into toner formulations such as those useful in printers and copiers.
Description
It is that the temporary patent application 60/758,757 and applying date on January 13rd, 2006 is the right of priority of the temporary patent application 60/663,422 on March 18th, 2005 that the application requires the applying date.
Be incorporated herein by reference in this content above two parts of temporary patent applications.
Background technology
In brief, need provide a kind of improved toning agent, positively chargeable or negative charge come to use in the duplicating machine of office usefulness and laser printer.The improvement of seeking be improve to flow and soak, usefulness is lower when melt energy, can be from the depleted paper in the office deinking and from renewable resources, obtain toner resin.Resin can provide negative charge to the performance of positively charged latent electrostatic image be to use the duplicating machine of such tinting system (toning system) and printer market common more the concern.Traditional toning agent is based on synthetic resins as styrene-acrylate, polyester, polymeric amide etc.Consider the long run supply that environment can bear, than the resin that is derived from oil, the resin that obtains as corn, soybean and other plant from renewable resources feed (feedstock) obtains paying close attention to more and more widely.From dipolymer acid and the acquisition of D-Isosorbide, it has good toning and the print characteristic that is similar to present petroleum resin keynote toner based on an example of the resin of biology.
The toning agent that comprises resin has a kind of demand that the ability of disperseing pigment also is present existence.Be derived from the vibrin based on biology of dipolymer acid and D-Isosorbide, use in the mode of powder coated, the pigment of the final coating that provides disperses to be improved.For resin, also exist it is flowed with the demand of the work energy consumption that minimizes duplicating machine in lower temperature of fusion.
Use replaces some petrochemical industry feeds to cause people's very big interest to be widely used in Application Areas based on the feed of biology.The evidence of this interest is reflected on the quantity of the relevant comment of delivering in the last few years.In vibrin synthetic, use trial based on the feed of biology in U.S. Pat 6,063, provided example in 464, wherein in the synthesizing of polyester material, used the Isosorbide that is derived from corn.
Relevant technology comprises U.S. Pat 5,959,066, US 6,025,061, US 6,063,464 Hes
Summary of the invention
Generally speaking, the invention provides a kind of toning agent with positive charge or negative charge.Described toning agent typically is used on electrostatic duplicating machine and the printer.
The first embodiment of the present invention provides a kind of toning agent that comprises pigment (coloring agent) and thermoplastic polymer.Typically, described toning agent comprises mean particle size less than 30 microns particle, is preferably mean particle size less than 25 microns particle, and preferably mean particle size is less than 20 microns particle.Typically, also used the vehicle of from following, selecting: charge control agent, flow control agent, lubricant, anticaking agent and various mixture thereof.In some typical embodiment, described toning agent has the negative friction electric charge of 10 to 40 microcoulomb/grams, and the triboelectric charge amount that is preferably with is 10 to 20 microcoulomb/grams.Exemplary embodiments more of the present invention provide a kind of toning agent with polymer glass invert point of 50 ℃ to 70 ℃.
In one embodiment of the invention, described toning agent uses with printer paper and copy paper.
In further embodiment of the present invention, provide a kind of method by pigment and thermoplastic polymer are mixed the toning agent of making electronegative or positive charge.The mixing of typical toning agent is included in the mixing of carrying out powder on the hot-rolling milling train, and the polymer resin that perhaps is used for toning agent is extruded with dispersive pigment.Typically, composite toning agent is by micronization, and if needs will carry out suitable screening to particle size dispersion according to being used for.
An alternative embodiment of the invention provides a kind of toning agent, comprises the amorphous thermoplastic polymer of selecting from following material: (1) carboxyl or hydroxyl-functional polyester; (2) polyester ether; (3) urethane (polyurethane); Wherein, described polymkeric substance is to obtain from least one monomer based on biology, and described polymkeric substance has 50 ℃ to 80 ℃ T
gB. pigment; And wherein, described toning agent comprises that mean particle size is less than 30 microns particle.In one embodiment, described carboxyl-functional polyester is to obtain from dihydroxyl hexitol group (for example, the group of Isosorbide), the first diacid group and/or the second diacid group, also optionally adds an acid.In a further embodiment, described Isosorbide group is a D-Isosorbide group, and described first diacid is a 1,4 cyclohexanedicarboxylic acid, and described second diacid is the long chain diacid that has 8 or more carbon atom in the chain.
A kind of toning agent that an alternative embodiment of the invention provides comprises the amorphous thermoplastic polymer of selecting from following material: (1) carboxyl or hydroxyl-functional polyester; (2) polyester ether; (3) urethane; Wherein, described polymkeric substance is to obtain from least one monomer based on biology, and described polymkeric substance has 50 ℃ to 80 ℃ T
gB. pigment; Wherein, described toning agent comprises that mean particle size is less than 30 microns particle.In one embodiment, described carboxyl-functional polyester is to obtain from dihydroxyl hexitol (dianhydrohexitol) group (for example, the group of Isosorbide), the first diacid group and/or the second diacid group, also optionally adds an acid.In a further embodiment, described Isosorbide group is a D-Isosorbide group, and described first diacid is a 1,4 cyclohexanedicarboxylic acid, and described second diacid is the long chain diacid that has 8 or more carbon atom in the chain.
In embodiment further, described toning agent comprises (1) thermoplastic polyester, and described thermoplastic polyester is the reaction product of following material: A. dihydroxyl hexitol; B. dimer diol and/or dimer diacid; C. diacid, diester or chlorination diacid; D. selectable catalyzer; (2) pigment.
In another embodiment, provide a kind of photographic developer, it comprises:
(1) thermoplastic polyester, described thermoplastic polyester comprises the reaction product of following material: A. dihydroxyl hexitol; B. dimer diol and/or dimer diacid; C. diacid, diester or chlorination diacid; Can select the catalyzer that uses with D.;
(2) pigment; With
(3) carrier.
In certain embodiments, described photographic developer comprises magnetic substance.
In further embodiment of the present invention, the image that provides the toning agent synthetics of the electronegative or positive charge that a kind of use comprises pigment and thermoplastic polymer to generate.
Description of drawings
Fig. 1 is with hard, the Isosorbide of crystalline state and the synthetic route schema that non-crystalline state dimer diol, aromatic diesters and other composition mix to come the synthesizing polyester material;
Fig. 2 mixes to come the synthetic route schema of synthesizing polyester acid with the Isosorbide of hard, crystalline state and non-crystalline state dimer diol and other composition, can be used in particular for toning agent;
Fig. 3 is with hard, the Isosorbide of crystalline state and the synthetic route schema that dimer diol, non-crystalline state dimer diacid, polymeric polyisocyanate (polyisocyanates) (for example, vulcabond) and other composition mix to come synthesis of polyurethane;
Fig. 4 is the typical monomers (1a, 1b and 1c) of useful in the present invention Isosorbide;
Fig. 5 is the synoptic diagram of the various parts of the present invention's device of being used to make resin examples 1 to 3F;
Fig. 6 is based on biological resin examples 1 and the rheological curves figure of 3C, and wherein transverse axis is tension force rate (1/ second), and the longitudinal axis is to be the viscosity degree of unit with pool (Poise), and these resins based on biology are the typical cases that are used for toning agent.
Embodiment
Always, the present invention will based on the use of biological feed with the demand based on the toning agent of biology is combined.Corn and soybean feed can be used to make the resin with the balance character that is suitable for the toning agent performance.These resins just can be made into the prescription (formulation) of various toning agents.
Typically, among the embodiment, be: main resin ground is become powder, carry out dry blending with the pigment of pulverizing, the selected additive of pulverizing according to the preparation method of toning agent of the present invention; Also can carry out extra micronization then.In a preferred embodiment, fluoropolymer resin be extruded after pigment mixes and micronization.But this mixture micronization or grind to form the granular size that needs, the toner powder of Sheng Chenging is screened at last obtains final granular size.In order to be coated onto in the substrate (substrate), general toning agent is mixed with carrier, and after coating, carrier generally can separate with substrate.
The said product based on biology of the present invention is meant that product is that the renewable resources that utilizes agricultural or forestry transforms with traditional chemically modified and/or the bioprocess as fermentation and obtains at least.Carbon source obtains from reproducible crop/trees resource, and unlike traditional limited exhausted mineral carbon source.
Many polymer properties very important for the toning agent performance are arranged, and the key property that wherein receives publicity has:
The aim parameter of negative or positive triboelectric charge is 10 to 40 microcoulomb/grams.Need just can produce acceptable copy greater than the negative or positive electric charge of 10 microcoulomb/grams, because image quality is the number affects that is subjected to electric charge.
Polymer glass invert point (T
g) aim parameter be 50 ℃ to 70 ℃.Acceptable fusing and blocked impedance (being the storage caking of toner powder) are subjected to T
gStrong influence.
The component of basic toning agent used herein is 10% carbon and 90% polymkeric substance.Yet, can select any desired ratio of pigment and polymkeric substance, be coated in suprabasil pigment and can keep as long as this toning agent provides required character such as adhesion, fusing to make.Other additive cited below can be included in and obtain needed toning agent performance in the typical toning agent, and according to instruction of the present invention, those skilled in the art can select additive and material to obtain the charge characteristic that needs.
The powder flowbility of Flow Control preparation-be used to provide.Example comprises fumed silica and the fine particle that has ground.
Surface additive-generally be that lubricant is used for preventing that toning agent is displaced to fusing cylinder, sanitising agent, frictional electrification lotus; Toning agent flows and controls; For example, in order to aerosil (R972), the titanium dioxide (P25) of stability that triboelectric charge is provided, as electric charge rate improving agent and as the stearic acid zinc salt of blade cleaning lubricants; Polyvinylidene difluoride (PVDF) (fluoropolymer) as slip additive.
Pigment-mineral black, for example, carbon black, magnetite or the mixture of the two; Add brilliant pigment, full gamut; Typical coloured pigment, the metal phthalocyanine dyestuff of cyan-replacement, magneta colour-quinacridone, azonapthol, aminofluorene (xanthene), the tetrazo growth of yellow-benzidine, Monoazo compound.
Dispersion agent-prevent or reduce pigment and assemble and provide pigment in toning agent, to launch more completely with additive.In the present invention, the dispersion agent of some resin usable as internal, for example material among the example 3F.
Weighting agent-fusing and release promotor, for example, wax.
Magnetic additive-generally be used for volume, extensibility, color, the cleaning of toning agent.
Conduction with insulating additive-generally the add electroconductibility that it controls toning agent.For example, can add the electroconductibility that silica is controlled carbon black.
Charge control agent-adding provides the suitable positive and negative and quantity of electric charge of triboelectric charge; Control electric charge rate; Fusing parameter and fusing time; For example, aerosil R972.
Be used for the present invention separately or comprise as joining the typical thermoplastic polymer (and monomer whose) that main component mix to use: polymeric amide, polyester, polyester ether, urethane, with mixing of CALCIUM ACRYLATE or polymeric amide, with and various mixture.Vinylbenzene composition in the polystyrene CALCIUM ACRYLATE can be used to control negative charge.Polystyrene CALCIUM ACRYLATE with higher vinylbenzene composition is mixed into the quantity that is expected to improve negative charge in the polymkeric substance of the present invention.
The mixture of using among the present invention can be the polymerization of homogeneous dispersive component or material largely; Typically, because one of them composition is a thermoplastic polymer, these components or material just fuse together.
The polymerization degree-after tested finds, best material is that the polymerization degree that has makes it that solid-state toning agent is provided when room temperature and changes rapidly when typical toning agent temperature.This material should flow on the paper or in other substrates easily, and is being heated to above its T
gAbove adhering well to during temperature.The typical polymerization degree comprises 5-80 unit.This material should not be crisp, in order to avoid fracture produces deleterious dust.
In addition, the mixing of the polymkeric substance of different molecular weight can be used to provide the fusing rheology of acceptable melting behavior needs.In each example of the present invention, the additive of use is through minimized.Generally, can add fumed silica and help flow of powder, to obtain good magnetic brush structure.Generally the basic toning agent component of Shi Yonging is 90% resin and 10% carbon black.Regal 330, RAVEN that Cabot company produces and carbon black are typical useful carbon blacks.
The resin that is particularly useful according to the present invention has good balance on the performance of two obvious contradictions:
Have low cement when (1) melting, flow out well when being convenient to apply, this is the characteristic of amorphous resin, but also must have;
(2) for the high relatively glass transition temp (T of good storage stability
g), be the characteristic of crystalline resin.If T
gToo low, powder particle meeting " soft ", and be agglomerated into useless agglomerate when preserving, especially when storage temperature is higher.Usually, these character are come balance by crystalline resin and amorphous resin are mixed into effective semi-crystalline state resin compound.The typical resins that obtains according to the present invention provides these required character.
Attention: unless mention especially, % is meant the mass percent (wt%) of this composition when the amount of certain composition of expression.
Disclosed resin synthetic method mainly contains three kinds:
1, the glycol that obtains based on dimer diol, from Isosorbide and/or the hydroxy functional group polyester of dipolymer acid.Generally, the carbonyl of polyester or hydroxy functional group are to be determined by the excess molar ratio that diacid or functionalized with glycols are rolled into a ball.Polyester typically comprises the bio-based composition of 5wt% net content at least, but modal be to comprise 20wt% to 50wt%.
2, the glycol that obtains based on dimer diol, from Isosorbide and/or the carboxyl functional group polyester of dipolymer acid.Generally, the carbonyl of polyester or hydroxy functional group are to be determined by the excess molar ratio that diacid or functionalized with glycols are rolled into a ball.Polyester typically comprises the bio-based composition of 5wt% net content at least, but modal be to comprise 50wt% to 70wt%.
The polyester polyol resin that disclose in this place is all useful in toning agent and pigment dispersion agent.
The present invention also is fit to be applied in each side with one or more these materials based on biology, includes but not limited to toning agent.The resin of an embodiment has the glass transition temp T less than 80 ℃
g, the resin among other embodiment has the glass transition temp T less than 70 ℃
g, the resin of some embodiment has the glass transition temp T less than 60 ℃ in addition
g, have suitable fusing rheological properties.Resin according to general embodiment of the present invention has minimum 20 ℃ glass transition temp and the highest 80 ℃ glass transition temp, and suitable fusing rheology is arranged.The useful resin of current control generally had lower glass transition temp (for example, T among the example 3B
gBe about 28.4 ℃), but this temperature is positioned at 20 ℃ to 80 ℃ scope.In certain embodiments, typical glass transition temp is 25 ℃ to 60 ℃.Has low T
gMaterial can with have high T
gMaterial mixing multiple character is provided.
Can include jointly a plurality of components Isosorbide (typically from the corn feed) and produce component such as the dipolymer acid or the dimer diol (typically from the vegetables oil feed) of softening effect for example that reacts, easily produces hardening effect according to resin of the present invention.With these component coreaction resins, the outflow of resin and storage stability all can be controlled by suitably.Usually, the sclerosis component comprises the chemical functional group, and for example alcohol, ester, carboxylic acid or acid chloride are attached to the movability that limits them on the ring texture; Yet the softening component comprises attached to the chemical functional group on the aliphatic carbon chain.Isosorbide is the glycol that comprises the cyclic ethers ring of fusing, is based on the member of biological carbohydrate derivative extended familys (being commonly referred to as the dihydroxyl hexitol).Poly-acid of two things and dimer diol are respectively dicarboxylic acid and glycol, from mainly being that aliphatic lipid acid based on biology obtains in essence.Similarly, these sclerosis and softening effect also can be applicable to as the urethane described in Fig. 3.
The present invention also relates to form the prescription of toning agent from one or more resins of the present invention.The peculiar property of a kind of embodiment of toning agent is the pigment dispersiveness that electronegative, good flowability, good meltability are become reconciled.
The key characteristic that is used for the resin of toner formulation is glass transition temp (T
g), it is typically at least 50 ℃, and for the storage stability of final toner powder, this temperature is preferably at least 60 ℃.The tabulation that table 1 has shown several resins based on soybean with and function and T
gThis table has shown from the monomer production based on soybean that comprises low cement to have acceptable T
gThe difficulty of resin.
| Table 1. is based on the resin of soybean | ||
| The resin numbering | Functional | T g(℃) (if detectable words) |
| R-1 | Amino amine | 61 |
| R-2 | Hydroxyl | 45 |
| R-3 | Hydroxyl | 28 |
| R-4 | 100% hydrogenant polyester polyol | The wax shape |
| R-5 | 50% hydrogenant polyester polyol | The wax shape |
| R-6 | Polyester | The wax shape |
Have only resin 1 to satisfy T
gStandard.In order to reach higher T
gAnd keep high in the resin based on biomaterial, use Isosorbide, had high intrinsic T
gOther material based on biology.
For example, higher T is arranged
gIdentified can the reaction jointly of the material based on biology (Isosorbide that from the corn feed, obtains) with material based on soybean, produce and have high composition and sufficiently high T based on biology
gResin to be used for toner formulation.Selected based on soybean material and other composition can reach in the resin and the balance of character in the final toning agent.
Synthetic (the seeing example 1 and 2) of resin:
Use and produce toning agent based on the material of biology and can followingly describe:
The preparation polyester polymers: (1) in reactor with Isosorbide (from the corn feed, obtaining), aliphatics dimer diol and/or dimer diacid (from the soybean feed, obtaining), diacid, diester or diacid chloride and optionally altogether glycol, optionally altogether diacid, altogether diester or altogether diacid chloride mix with the catalyst concentration of suitable polymerizable aromatic diacid and glycol; (2) heat this monomer and catalyzer monomer polymerization is produced polyester (referring to Fig. 1).
Preparation carboxyl-functional polyester resin: (1) in reactor with Isosorbide, aliphatics dimer diacid, optionally altogether diacid, altogether diester or altogether diacid chloride and optionally altogether glycol mix with catalyst concentration; (2) heat this monomer and catalyzer monomer polymerization is produced carboxyl-functional polyester resin (referring to Fig. 2).
The preparation of hydroxyl, carboxyl or isocyanate-functional urethane: the catalyzer that is suitable for polymer diol and diacid and polymeric polyisocyanate is added or do not added in (1) with Isosorbide, aliphatics dimer diacid and/or dimer diol, polymeric polyisocyanate, optionally totally two pure and mild optionally diacid, diester or diacid chloride mixing altogether altogether altogether, in reactor; (2) heating monomer and optional catalyzer produce urethane (referring to Fig. 3) with monomer polymerization.
With reference to figure 1,2,3, useful in embodiments of the present invention various reactants have been disclosed.Except the dimer diol and dipolymer acid that are disclosed, embodiment widely of the present invention comprises the aliphatic chain that has 4 to 20 carbon atoms usually.Preferably, this aliphatic chain has 6 to 16 carbon atoms.
Dimer diol of Jie Shiing and dipolymer acid comprise six-ring in addition, and two side chain is the aliphatic side chains with 4 to 20 carbon atoms, and two side chains have 8 to 12 carbon atoms and have hydroxyl or carboxyl functional group in addition.
In addition, diester, diacid, common diacid and common diester have general formula R
2-CO-R
1-CO-R
2, R wherein
2=-OH ,-OR
3Or-Cl, wherein R
3=have an aliphatic chain of 1 to 4 carbon atom.R
1Can be aryl or fatty group with 2 to 12 carbon atoms.
Though without wishing to be held to the border of theory, the present invention believes that the aliphatic side chains in dipolymer acid and dimer diol provides low cement to resin.Aliphatic side chains is easy to soften when low temperature, causes lower cement and better mobile.Chain is long more, can see more that it is softer, and softening sooner when heating.
As shown in Figure 9, the present invention can provide the pigment that has improved to disperse in certain embodiments.A better mobile result is exactly the better wetting of pigment, therefore can improve the dispersiveness of pigment.
In addition more generally, the dihydroxyl hexitol can be with in the present invention.Therefore, when the method with the dicyclo that comprises other cyclic alcohol prepared hardening structure, other dihydroxyl hexitol can replace D-Isosorbide or its isomer with in the present invention.Glycol coupling collar hexyl, isophorone and other ring structure can increase the hardening effect that is similar to Isosorbide.
Dimer diacid is typically to use C
18The viscous liquid that the dimerization of unsaturated fatty acids produces.C
18Unsaturated fatty acids has three kinds of biogenetic derivations, i.e. plant, Yatall MA and animal.C
18The unit can several modes link together.4 kinds of main structure types are because of main component C
36Diacid and known, promptly acyclic, monocyclic, dicyclo with fragrance.At every kind of structure type many isomer are arranged also.The list or many-the processing condition that unsaturated ratio and dimerization adopted of the lipid acid feed of beginning are depended in the distribution of these structure types and isomer.The dimer diacid of the minimum of Shi Yonging is C in certain embodiments
18Diacid.
Four types dimer diacid all can be buied on market: (not the purifying) of (1) standard comprises 80% C
36Diprotic acid; (2) purified wherein C
36Diprotic acid content is brought up to 92-98%; (3) purify and partial hydrogenation to improve color; (4) purify and fully hydrogenation to reach maximum stable.
The dipolymer acid that is used for preparing based on the vibrin of biology is Empol 1018
(example 3 and 3C) and Pripol
(example 2), the both is based on the dipolymer acid of plant.Empol 1018
Be that Cognis company produces Pripol
Be that Uniqema company produces.Cognis has stopped their production based on the dimer diacid of plant, more glad production Yatall MA.Table 1A has compared Pripol 1013
And Empol1018
Physical properties and composition.Pripol 1013
Color is more shallow and have higher diprotic acid content.The carboxyl-functional resin made from these two kinds different dipolymer acid has similar physical properties.
The composition and the character of the acid of table 1A. dipolymer
| Dipolymer acid | Empol 1018 (lot numbers: U42G151910) | Pripol 1013 (lot numbers: 091687) |
| The acid number color, Gardner's composition wt% monoprotic acid wt% diprotic acid wt% polyprotonic acid | 193.5 8 5 81 14 | 195 3-4 0.1 97 3 |
Dimer diol generally makes by the dimer diacid methyl ester is carried out high-pressure hydrogenation.The dimer diol that is used for preparing the vibrin (example 1,1A and 3B) based on biology is SPEZIOL C36/2 1075
Dimer diol.This is the dimer diol based on plant of being produced by Cognis company.
Disclosed resin is in case the fusing back has lower cement (seeing example) with respect to the resin based on petroleum chemicals on the market.In toner formulation, need to add flowable material (Flow Control preparation) and reach good fusing and other acceptable copy character.Based on the resin of biology only need seldom or do not need such additive just can reach good film grade and outward appearance.Also can in the prescription that comprises traditional resin based on petroleum chemicals, be used as flowing additive based on the resin self of biology.
Polyester polymers of the present invention by with Isosorbide, dimer diol and/or dipolymer acid, diacid, diester or diacid chloride, optionally totally two pure and mild optionally altogether diacid, altogether diester or altogether diacid chloride fusing polymerization make (method among Fig. 1)
The typical process that is used for preparing the hydroxyl-functional polyester has description in example 1.Aliphatic polyester is soft, flexible elastomeric material.Most aromatic polyesters are crystalline state.The Isosorbide of soft dimer diol and height functionalization mixed and mix and to obtain having the superperformance balance with the crystalline state aromatic diacid.Yet this balance also can promote (being " glycol " of Fig. 1 and 2) by other material of adding such as ethylene glycol in reaction.
By at glass transition temp (T
g) for scope prepares polyester various monomeric effects have been carried out studying (table 2A and 2B) from 61 ℃ to 165 ℃.Table 2A has showed the typical properties and the glass transition temp (T that has from 61 ℃ to 165 ℃ of the method synthetic resin that the application describes
g) various monomeric effect.
Table 2B has showed the typical properties according to the description synthetic carboxyl-functional resin of example 2-3.
| The polyester polyol of the Isosorbide that dimer diol that table 2A. extracts based on soybean and/or corn extract | ||||||||
| Example | Dimer diol (mole %) a | Isosorbide (mole %) | Ethylene glycol (mole %) | Dimethyl terephthalate (DMT) (mole %) | T g(℃) | Inherent viscosity (dl/g) b | Hydroxyl value (mg KOH/g) | Acid number (mg KOH/g) |
| Example 1 | 5.8 | 14.9 | 27.8 | 51.5 | 61 | 0.29 c | 23.3 | 8.0 |
| Example 1A | 12.2 | 38.0 | 0 | 49.8 | 165 | 0.10 | 40.9 | 2.6 |
| Example 3B | 10.8 | 17.1 | 22.7 | 49.4 | 28.4 | 0.19 | 35.4 | 6.1 |
| Annotate: aBe based on that the NMR of final resin calculates and be molar percentage based on the vibrin composition % of dimer diol; bIn room temperature is 25 ℃, and the polyester liquid of 1% (mass/volume) measures in ortho chloro phenol; CIn ortho chloro phenol, have only 92% solvable ND=not measure. | ||||||||
| The polyester polyol of the Isosorbide that dimer diol that table 2B extracts based on soybean and/or corn extract | |||||||
| Example | Dipolymer acid (wt%) a | Isosorbide (wt%) | 1,4CHDA (wt%) | T g(℃) | Inherent viscosity (dl/g) b | Hydroxyl value (mg KOH/g) | Acid number (mg KOH/g) |
| Example 2 | 19.4 | 37.1 | 43.4 | 64.2 | ND | ND | 34.8 |
| Example 3 | 16.1 | 38.4 | 45.5 | 66.9 | 0.25 | 13.0 | 36.3 |
| Annotate: aBe based on that the NMR of final resin calculates and be molar percentage based on the vibrin % of dimer diol; bIn room temperature is 25 ℃, and the polyester liquid of 1% (mass/volume) measures in ortho chloro phenol; ND=does not measure. | |||||||
Data presentation use these monomeric T
gPossible big scope.The test polyester that does not use Isosorbide and prepare is not non-crystalline state, comprises Isosorbide unlike those, but crystalline state.
D-Isosorbide (1,4:3,6-two dehydration-D-sorbitols) (1a) or its isomer and/or comprise all mixture of isomers of D-Isosorbide can replace the D-Isosorbide to use.1,4:3,6-two dehydration-D-N.F,USP MANNITOL (1b) (1,4:3,6-dianhydro-D-mannitol) with 1,4:3, (1,4:3 6-dianhydro-D-iditol) is two isomer of Isosorbide to 6-two dehydration-D-iditol.The D-Isosorbide is with in the present invention, but the isomer of D-Isosorbide also can use.The isomer that can be used for Isosorbide of the present invention has displaying in Fig. 4.
The polyvalent alcohol of suitable formation acid functional polyester comprises: 1,2-ethylene glycol, 1, ammediol, 1,4-butyleneglycol, 1,6-hexylene glycol, 1,10-certain herbaceous plants with big flowers glycol, 1,12-lauryl alcohol, 1,4 cyclohexane dimethanol, glycol ether, triglycol, neopentyl glycol, three methanol-based propane, Hydrogenated Bisphenol A (2,2-(dicyclohexyl) propane), 2,2,4-trimethylammonium-1-1,3-pentanediol, 2-methyl isophthalic acid, ammediol, 2-methyl-2-methylol-1, ammediol, 2-ethyl-2-methylol-1, ammediol and analogue and comprise the combination of at least a aforementioned polyvalent alcohol.Because the target of current work is to improve the content of biomass, preferred polyhydric alcohols is the polyvalent alcohol of character that can be used for improving needs of the sour glycol (from the soybean feed) of Isosorbide (from the corn feed) and dipolymer, ethylene glycol and other.
Suitable polycarboxylic acid, acid esters and acid chloride, comprise that those are from succsinic acid, lipid acid, nonane diacid, sebacic acid, 1,12-laurostearic acid, terephthalic acid, m-phthalic acid, trimesic acid, Tetra Hydro Phthalic Anhydride, hexahydrophthalic acid, 1,4 cyclohexanedicarboxylic acid, trihemellitic acid, naphthalic acid, dimeracid and analogue and comprise that at least a aforementioned polycarboxylic acid's compound obtains.Preferred diester is the dimethyl esters of terephthalic acid.Dodecanedioic acid (DDA) is as the modifier in several prescriptions.Diacid such as 1,4 cyclohexanedicarboxylic acid, Empol 1018
, Pripol 1013
And analogue also can use.Preferred diacid has long-chain provides flexible, so the dipolymer acid that has 8 or more carbon atom in the chain is for first-selected.
In order to obtain having the carboxyl-functional polyester of expection molecular weight, it is suitably more than hydroxy functional group to be used for forming the carboxyl functional group that has in the monomer mixture of this polyester, and the ratio of hydroxyl equivalent and acid equivalent generally is 0.85-0.95.This polyester normally is a non-crystalline state.
With reference now to Fig. 5,, this figure has shown each parts of the device 100 that is used for making resin according to the present invention.Heating mantles 102 is covering reactor 101 at least in part, is used for controlling packet to contain the temperature of the reactor 101 of reaction mixture 104.Reactor 101 comprises reaction vessel 106 and lid 108.Lid 108 has a plurality of necks 110,112,114,116 and connects each device.Stirring is to be provided by the impeller 120 (for example, being typically the blade of 45) at the end of stir shaft 122 (for example stainless steel).Stir shaft 122 passes neck 116.The thermopair controller 130 that is connected to thermopair 132 by junctor 131 passes neck 110 at Inlet gas connector 111 places of sealing assembling and enters into reaction mixture 104.Vigreaux column (Vigreaux column) 140 sealings are assemblied on the neck 144.Thermometer 141 or other temperature measuring equipments are assemblied in the top (distillation plant) 142 of Vigreaux column 140.Condenser 150 uses junctor 146 to be linked and packed at neck 144 places of Vigreaux column 140 by condenser inlet 152.Vigreaux column 140 can by sheath around separate unit or sheath and post be one.The neck that condensator outlet 154 is connected neck 160 162 places that enter the mouth, this neck 160 also has air outlet 164, neck outlet 166.Receive flask 170 inlet 172 that is connected to neck outlet 166 is arranged.Cooling fluid 155 enters condenser 150 at inlet 156 places, and discharges in outlet 158.
In operation, argon gas 111-1 enters at inlet mouth junctor 111 places with covering reaction mixture 104, and 164 outflows from the air outlet.Various compositions can add or pass through hermetically-sealed connector 118 addings at neck 112 places before this device is closed.Attention is in Fig. 5, and neck 112 is located immediately at after the neck 116.Neck 112 is positioned on the axis 190 of reactor 101.Overhead product 178 is collected in and receives in the flask 170.
Below example be to the illustrating of each side of the present invention, be not to limit the scope of the invention in any manner.
The production of resin (example 1 is to example 3F)
Example 1
This example has been showed the production based on the hydroxyl-functional vibrin of biology.
The equipment (see figure 5):
Vigreaux column, distillation plant, the air inlet of 1 liter 4 neck cylindrical wall round bottom glass flask, band sheath goes out impeller, condenser and the reception flask of airway adaptor, stainless steel stir shaft and 4 blades (45 degree).Flow process:
The dimethyl terephthalic acid of in reactor, packing into ester (DMT) (228.30g, 1.1757 moles), Speziol C36/2 1075
Dimer diol (lot number #415252) (77.61g, 0.1411 D-Isosorbide (123.90g mole),, 0.84785 ethylene glycol (EG) (102.81 mole),, 1.6563 the mole), and then add four hydration manganous acetates (II) (0.0917g), four hydration cobaltous acetates (II) (0.0618g), weisspiessglanz (III) (0.103g).Cover with argon gas in the reactor.Then, with the reaction mixture under 1,2,3,4-tetralin (2ml) the adding argon gas.The temperature of each composition is warming up to 200 ℃ by stir (after the solid fusing) under argon gas in the reactor.This temperature maintenance 30 minutes.Reaction mixture is heated to 250 ℃ (1.6 ℃/minute) in during 30 minutes lentamente.This temperature maintenance 30 minutes or the temperature up to the Vigreaux column top drop to 30 ℃ or lower.When being heated to about 150 ℃, reaction collects methyl alcohol serially.When the vertical temperature of Vigreaux column descended, expression methyl alcohol was removed.Approximately the methyl alcohol of 95ml is distilled out.Then, the solution of adding Tripyrophosphoric acid (0.0634g) is added in the reaction mixture in EG (1g).The flow velocity of argon gas on the detecting reactant, and reduce to lower flow velocity when needed and avoid heating up in a steamer of Isosorbide.To slowly be heated to 280 ℃ (0.25 ℃/minute) in reaction mixture is during 2 hours.The overhead product receptor replaces with evacuated receiver, and vacuum is (＜1 holder) of using gradually.At this moment, ethylene glycol is distillated (91g), and the polymkeric substance of lower molecular weight has just formed.Reaction mixture temperature was kept 3 hours 10 minutes at 280 ℃.Reaction stops to keep normal atmosphere with argon gas covering reactant.Then reaction mixture is cooled to≤250 ℃ and be poured over and fluoridize on the fiber glass plates.
The resin of producing has following character:
Solution inherent viscosity: 0.29 (solvent is an ortho chloro phenol, only have 92% solvable)
T
g＝61℃
Hydroxyl value=24.3
Acid number=8.0
Molecular weight (MW)=3470 (calculating) with acid number and hydroxyl value
Polymer features:
Color: brown
Tackiness: not sticking
Transparency: slightly transparent
Flexible: crisp
Solid-state
Example 1A
This example has been showed the production based on the vibrin of biology.
The equipment (see figure 5):
Vigreaux column, distillation plant, the air inlet of 1 liter 4 neck cylindrical wall round bottom glass flask, band sheath goes out impeller, condenser and the reception flask of airway adaptor, stainless steel stir shaft and 4 blades (45 degree).
Flow process:
The dimethyl terephthalic acid of in reactor, packing into ester (DMT) (197.74g, 1.0183 moles), D-Isosorbide (119.05g, 0.81463 mole), Speziol C36/2 1075
Dimer diol (lot number #415252) (112.06g, 0.20371 mole) then adds 1,2,3,4-tetralin (2ml) and weisspiessglanz (III) (0.089g).Cover with argon gas in the reactor.The temperature of reactor is warming up to 200 ℃ by stir (after the solid fusing) under argon gas.This temperature maintenance 12 minutes.Reaction mixture is heated to 250 ℃ (2.5 ℃/minute) in during 20 minutes lentamente.This temperature maintenance 8 minutes.When being heated to about 150 ℃, reaction collects methyl alcohol serially.When the vertical temperature of Vigreaux column descended, expression methyl alcohol was removed.The methyl alcohol of nearly 83ml is distilled out.The flow velocity of argon gas on the detecting reactant, and reduce to lower flow velocity when needed and avoid heating up in a steamer of Isosorbide.Reaction mixture slowly is heated to 280 ℃ (2.3 ℃/minute) in during 13 minutes.Then, reaction mixture is cooled to 260 ℃.Extra D-Isosorbide (14.87g, 0.1018 mole) is added in the reaction mixture.Reaction mixture is heated to 280 ℃.Kept this temperature 30 minutes.The overhead product receptor replaces with evacuated receiver, and vacuum is (≤9 holder) of using gradually.At this moment, form the polymkeric substance of lower molecular weight.With this reaction mixture 280 ℃ temperature maintenance 2 hours 40 minutes.Reaction is to keep normal atmosphere with argon gas covering reactant and to stop.Then reaction mixture is cooled to≤250 ℃ and be poured over and fluoridize on the fiber glass plates.
The resin of producing has following character:
Solution inherent viscosity: 0.10 (solvent is an ortho chloro phenol)
T
g＝165℃
Hydroxyl value=45.0
Acid number=2.3
Molecular weight (MW)=2372 (calculating) with acid number and hydroxyl value
Polymer features:
Color: light brown
Tackiness: viscosity
Transparency: transparent
Flexible: somewhat crisp
Solid-state
Example 2
This example has been showed the production based on the carboxyl-functional polyester resin of biology.
The equipment (see figure 5):
Vigreaux column, distillation plant, the air inlet of 5 liters 4 neck round bottom glass reaction containers, band sheath goes out impeller, condenser and the reception flask of airway adaptor, stainless steel stir shaft and 4 blades (45 degree).
Flow process:
D-Isosorbide (1337.0g, 9.1490 moles) (as what receive), Pripol 1013 pack in reactor
(1,4-CHDA) (1563.8g, 9.0826 moles) then add weisspiessglanz (III) (1.231g) for dipolymer acid (lot number #091687) (699.1g, 1.215 moles), 1,4 cyclohexanedicarboxylic acid.Cover with argon gas in the reactor.Then, 1,2,3,4-tetralin (2ml) is joined in the reaction mixture under the argon gas.The temperature of mixture is warming up to 200 ℃ by stir (after the solid fusing) under argon gas in the reactor.Kept this temperature 30 minutes.Reaction mixture is heated to 250 ℃ (1.1 ℃/minute) in during 47 minutes lentamente.This temperature maintenance 3.1 hours or drop to 30 ℃ or lower up to the head temperature of Vigreaux column.When being heated to about 180 ℃, reaction collects water serially.When the vertical temperature of Vigreaux column descends, represent that most water remove.Approximately the water of 329ml is distilled out.The flow velocity of argon gas on the detecting reactant, and reduce to lower flow velocity when needed and avoid heating up in a steamer of Isosorbide.Reaction mixture slowly is heated to 280 ℃ (0.25 ℃/minute) in during 2 hours.The overhead product receptor replaces with evacuated receiver, and vacuum is (＜1 holder) of using gradually.At this moment, residual water is distillated, and the polymkeric substance of lower molecular weight has just formed.With reaction mixture 280 ℃ temperature maintenance 3 hours 10 minutes.Reaction is to keep normal atmosphere with argon gas covering reactant and to stop.Then reaction mixture is cooled to≤250 ℃ and be poured over and fluoridize on the fiber glass plates.
The resin of producing has following character:
T
g＝64.2℃
Acid number=34.8
Molecular weight (MW)
GPC (polystyrene standard) M
n=1689
GPC (polystyrene standard) M
w=11681
Polymolecularity (M
w/ M
n)=6.91
Polymer features:
Color: light amber
Tackiness: not sticking
Transparency: transparent
Flexible: crisp
Solid-state
Example 3
This example has been showed the production based on the carboxyl-functional polyester resin of biology.
The equipment (see figure 5):
Vigreaux column, distillation plant, the air inlet of 1 liter 4 neck cylindrical wall round bottom glass flask, band sheath goes out impeller, condenser and the reception flask of airway adaptor, stainless steel stir shaft and 4 blades (45 degree).
Flow process:
In reactor, pack into 1,4 cyclohexanedicarboxylic acid (1,4-CHDA) (204.66g, 1.1886 moles), Empol 1018
Dipolymer acid (lot number #U42G151910) (72.54g, 0.1251 mole) and D-Isosorbide (172.80g, 1.1824 moles) then add weisspiessglanz (III) (0.1594g).Cover with argon gas in the reactor.Then, 1,2,3,4-tetralin (2ml) is joined in the reaction mixture under the argon gas.The temperature of reactor is warming up to 200 ℃ by stir (after the solid fusing) under argon gas.Kept this temperature 30 minutes.Reaction mixture is heated to 250 ℃ (1.6 ℃/minute) in during 30 minutes lentamente.This temperature maintenance 30 minutes or the temperature up to the top of Vigreaux column drop to 30 ℃ or lower.When being heated to about 180 ℃, reaction collects water serially.When the vertical temperature of Vigreaux column descends, represent that most water remove.Approximately the water of 47ml is distilled out.The flow velocity of argon gas on the detecting reactant, and reduce to lower flow velocity when needed and avoid heating up in a steamer of Isosorbide.Reaction mixture slowly is heated to 280 ℃ (0.25 ℃/minute) in during 2 hours.The overhead product receptor replaces with evacuated receiver, and vacuum is (＜1 holder) of using gradually.At this moment, residual water is distillated, and the polymkeric substance of lower molecular weight has just formed.Reaction mixture was 280 ℃ temperature maintenance 3 hours 10 minutes.Reaction is to keep normal atmosphere with argon gas covering reactant and to stop.Then reaction mixture be cooled to≤250 ℃ and be poured over and fluoridize on the fiber glass plates.
The resin of producing has following character:
Solution inherent viscosity: 0.25dl/g (solvent is an ortho chloro phenol)
T
g＝66.9℃
Hydroxyl value=13.0
Acid number=36.3
Molecular weight (MW)
GPC (polystyrene standard) M
n=2995
GPC (polystyrene standard) M
w=9560
Polymolecularity (M
w/ M
n)=3.19
Polymer features:
Color: light brown
Tackiness: not sticking
Transparency: most of transparent
Flexible: crisp and hard
Solid-state
Example 3B
This example has been showed the production based on the hydroxyl-functional vibrin of biology.
The equipment (see figure 5):
Vigreaux column, distillation plant, the air inlet of 1 liter 4 neck cylindrical wall round bottom glass flask, band sheath goes out impeller, condenser and the reception flask of airway adaptor, stainless steel stir shaft and 4 blades (45 degree).
Flow process:
The dimethyl terephthalic acid of in reactor, packing into ester (DMT) (228.30g, 1.1757 moles), Speziol C36/2 1075
Dimer diol (lot number #415252) (129.40g, 0.23523 D-Isosorbide (123.90g mole),, 0.84785 ethylene glycol (EG) (89.66g mole),, 1.444 the mole), then add four hydration manganous acetates (IIA) (0.0917g), four hydration cobaltous acetates (II) (0.0618g), weisspiessglanz (III) (0.103g).Cover with argon gas in the reactor.Then, 1,2,3,4-tetralin (2ml) is joined in the reaction mixture under the argon gas.The temperature of reactor is warming up to 200 ℃ by stir (after the solid fusing) under argon gas.Kept this temperature 30 minutes.Reaction mixture is heated to 250 ℃ (1.6 ℃/minute) in during 30 minutes lentamente.This temperature maintenance 30 minutes or drop to 30 ℃ or lower up to the head temperature of Vigreaux column.When reaction is heated to about methyl alcohol of collecting serially more than 150 ℃ the time.When the vertical temperature of Vigreaux column descends, represent that most methyl alcohol remove.Approximately the methyl alcohol of 95ml is distilled out.Then, be added in EG (1g) and be dissolved with the solution of Tripyrophosphoric acid (0.0634g) in reaction mixture.The flow velocity of argon gas on the detecting reactant, and reduce to lower flow velocity when needed and avoid heating up in a steamer of Isosorbide.Reaction mixture slowly is heated to 280 ℃ (1 ℃/minute) in during 30 minutes.The overhead product receptor replaces with evacuated receiver, and vacuum is (＜1 holder) of using gradually.At this moment, ethylene glycol is distillated (84g), and the polymkeric substance of lower molecular weight has just formed.Reaction mixture was 280 ℃ temperature maintenance 3 hours 10 minutes.Reaction is to keep normal atmosphere with argon gas covering reactant and to stop.Then reaction mixture be cooled to≤250 ℃ and be poured over and fluoridize on the fiber glass plates.
The resin of producing has following character:
Solution inherent viscosity: 0.19 (solvent is an ortho chloro phenol)
T
g＝28.4℃
Hydroxyl value=35.4
Acid number=6.1
Molecular weight (MW)=2700 (calculating) from acid number and hydroxyl value
Polymer features:
Color: brown
Tackiness: not sticking
Transparency: most of transparent
Flexible: crisp
Solid-state
Example 3C
This example has been showed the production based on the hydroxyl-functional vibrin of biology.
The equipment (see figure 5):
Vigreaux column, distillation plant, the air inlet of 1 liter 4 neck cylindrical wall round bottom glass flask, band sheath goes out impeller, condenser and the reception flask of airway adaptor, stainless steel stir shaft and 4 blades (45 degree).Flow process:
The dimethyl terephthalic acid of in reactor, packing into ester (DMT) (213.96g, 1.1018 moles), Empol 1018
Dipolymer acid (lot number #U42G151910) (71.02g, 0.1225 D-Isosorbide (128.79g mole),, 0.88128 ethylene glycol (EG) (116.28g mole),, 1.8734 the mole), then add four hydration manganous acetates (IIA) (0.0859g), four hydration cobaltous acetates (II) (0.0579g), weisspiessglanz (III) (0.0965g).Cover with argon gas in the reactor.Then, 1,2,3,4-tetralin (2ml) is joined in the reaction mixture under the argon gas.The temperature of reactor is warming up to 200 ℃ by stir (after the solid fusing) under argon gas.Kept this temperature 30 minutes.Reaction mixture is heated to 250 ℃ (1.6 ℃/minute) in during 30 minutes lentamente.This temperature maintenance 30 minutes or drop to 30 ℃ or lower up to the head temperature of Vigreaux column.When reaction is heated to about methyl alcohol of collecting serially more than 150 ℃ the time.When the vertical temperature of Vigreaux column descends, represent that most methanol/water mixture remove.Approximately the methanol/water mixture of 93ml is distilled out.Then, be added in be dissolved with Tripyrophosphoric acid (0.0594g) among the EG (1g) solution in reaction mixture.Also reduce to lower flow velocity when needed avoids heating up in a steamer of Isosorbide to the flow velocity of argon gas on the detecting reactant.Reaction mixture slowly is heated to 280 ℃ (0.25 ℃/minute) in during 2 hours.The overhead product receptor replaces with evacuated receiver, and vacuum is (＜1 holder) of using gradually.At this moment, ethylene glycol is distillated (95g), and the polymkeric substance of lower molecular weight has just formed.Reaction mixture was 280 ℃ temperature maintenance 3 hours 10 minutes.Reaction is to keep normal atmosphere with argon gas covering reactant and to stop.Then reaction mixture be cooled to≤250 ℃ and be poured over and fluoridize on the fiber glass plates.
The resin of producing has following character:
Solution inherent viscosity: 0.23 (solvent is an ortho chloro phenol)
T
g＝58.8℃
Hydroxyl value=23.7
Acid number=1.4
Molecular weight (MW)=4470 (calculating) from acid number and hydroxyl value
Polymer features:
Color: light brown
Tackiness: not sticking
Transparency: somewhat transparent, slightly dim
Flexible: crisp
Solid-state
Example 3F (pigment dispersing agent)
This example has been showed the production based on the carboxyl-functional polyester resin of biology.
The equipment (see figure 5):
Vigreaux column, distillation plant, the air inlet of 2 liters 4 neck round bottom glass reaction containers, band sheath goes out impeller, condenser and the reception flask of airway adaptor, stainless steel stir shaft and 4 blades (45 degree).
Flow process:
D-Isosorbide (545.35g, 3.7317 moles) (as what receive), Pripol 1013 pack in reactor
(1,4-CHDA) (632.49g, 3.6734 moles) then add weisspiessglanz (III) (0.498g) for dipolymer acid (lot number #091687) (272.17g, 0.47302 mole), 1,4 cyclohexanedicarboxylic acid.Cover with argon gas in the reactor.Then, add in the reaction mixture of 1,2,3,4-tetralin (2ml) under the argon gas.The temperature of reactor is warming up to 200 ℃ by stir (after the solid fusing) under argon gas.Kept this temperature 30 minutes.Reaction mixture is heated to 250 ℃ (1.6 ℃/minute) in during 30 minutes lentamente.This temperature maintenance 2.1 hours.When reaction is heated to about water of collecting serially more than 180 ℃ the time.When the vertical temperature of Vigreaux column descends, represent that most water remove.Approximately the water of 134ml is distilled out.The flow velocity of argon gas on the detecting reactant, and reduce to lower flow velocity when needed and avoid heating up in a steamer of Isosorbide.Reaction mixture slowly is heated to 280 ℃ (0.25 ℃/minute) in during 2 hours.The overhead product receptor replaces with evacuated receiver, and vacuum is (＜1 holder) of using gradually.At this moment, residual water is distillated, and the polymkeric substance of lower molecular weight has just formed.Reaction mixture was 280 ℃ temperature maintenance 30 minutes.Reaction is to keep normal atmosphere with argon gas covering reactant and to stop.Then reaction mixture be cooled to≤250 ℃ and be poured over and fluoridize on the fiber glass plates.
The resin of producing has following character:
T
g＝52.9℃
Viscosity number in the time of 120 ℃=7772 pools
Viscosity number in the time of 160 ℃=247 pools
Polymer features:
Color: Huang/light amber
Tackiness: not sticking
Transparency: transparent
Flexible: crisp
Solid-state
Following example formulation 1 to 6 has been showed according to several typical toner formulation of the present invention.
Prescription 1
Prepare toning agent with the vibrin that makes from Isosorbide (extract from corn) and dimer diol (extraction) in the example 1 and the carbon black of Cabot company production from soybean.
It is found that polyester toner based on biology is than the more difficult micronization of the toning agent of the original equipment manufacturer of standard.This mainly is because based on the higher molecular weight that has of the polyester of biology.Generally, toning agent has the mean particle size less than 30 microns.Mean particle size based on the polyester toner (resin adds pigment) of biology is 24 microns.Yet, the vibrin based on biology not being added in the micronization test of carbon black at another, granular size has been reduced to 14 microns.This expression resin itself is machinable.
Table 1. is based on the polyester toner resins (comprising dimer diol) of biology
Developer formuia
Polyester toner 1.143g based on biology
Carrier FC-2 (being coated with the silica sand of methyl terpolymer) 17.862g
Degussa R-972 (charge control agent) 0.011g
The average friction electric charge is-11.2 microcoulomb/grams.The mixing of pigment is the resin of 90wt% and the carbon black of 10wt%.
Prescription 2
Prescription with the preparation of the resin among example 3C toning agent.90g was mixed 20 to 30 minutes with the treatment temp of 285-300 on Thropp 2 steam rolling mills with 10g Raven 5210 CB from the resin based on soybean that example 3C obtains.From 2 rolling mills, will recapture the mixing material of about 98.98g.
With this mixing material fragmentation, mix cooling with dry ice then.Material collects to carry out micronization by hammer mill 1 and the sieve by 10mil.The material of recapturing from hammer mill 1 has 50.56g (annotate: some material spills) when recapturing.Use Sturtevant air mill (model Mikropul#630) in the grinding pressure of 87psi, the feeding pressure of 70psi and No. 3 settings on the vibrating feed dish then, the toning agent that hammer mill was handled is micronized to suitable granular size (＜20 microns mean sizes).Material feed rate approximately is 0.14 gram/minute.
The mean particle size of toner formulation is 11.7 microns mean diameter on the volume, quantitatively is 3.4 microns.
Photographic developer is that 4% micronized resin and carbon black prepare with the FC-2 carrier with concentration in carrier.Toner formulation 2 is mixed available average friction electric charge with carrier be about 14.2 microcoulomb/grams.Estimate the image that resin has abundant negative charge just can produce.
The toning agent of making by the resin among the D type duplicating machine Shire usage example 3C based on soybean just can produce image.
The preparation of prescription 3
Mix with Raven 5250 CB of 10 grams from the 90 gram carboxyl official soy resins that example 2 obtains, follow same treatment condition and step in the prescription 2, just be expected to obtain and the 2 similar electronegative toning agents of filling a prescription.
The preparation of prescription 4
This example has been showed the toning agent of band negative friction electric charge.The 90 gram carboxylic officials that obtain from example 3 can soy resins mix with Raven 5250 CB of 10 grams, follow the same treatment condition and the step of preparation prescription 2, just are expected to obtain and the 2 similar electronegative toning agents of filling a prescription.
The preparation of prescription 5
This example has been showed the preparation with the toning agent of positive triboelectric charge.
The 90wt% resin that obtains from example 1 and the carbon black of 10wt% (from Cabot company) mix mutually with the 2 same conditions of filling a prescription in Thropp 2 rolling mills, make toning agent.Toning agent grinds with following condition in the Sturtevant shredder: the feeding pressure of 60psi, the grinding pressure of 90psi and delivery rate are 0.2 gram/minute.
Used FBF-300 carrier (Powdertech company limited).The core material of this carrier is cupric oxide (～14%), zinc oxide (～15%), ferric oxide (～71%) and coats with silicone resin.This carrier mixes with toning agent on the rolling shredder.The amount of carrier and type can be regulated and be controlled and obtain required triboelectric charge.
So just, can obtain having the average positive triboelectric charge toning agent of+3.6 microcoulomb/grams approximately.Though the quantity of electric charge of band is lower than expection, can use charge control agent to promote.
Developer formuia 1
This example has been showed the preparation and the use of photographic developer, for example is used in combination with duplicating machine with using electronegative carrier and toning agent.
The toning agent that uses in this example makes according to prescription 2.The material that is used for photographic developer is the FC-2 carrier of 200.0 grams, the micronization toner formulation of 8.0 grams and the Aeorosil R-972 charge control agent of 0.0418 gram.Resulting average friction electric charge is-13.9 microcoulomb/grams.
Photographic developer is used for producing image by D type duplicating machine Shire.Image conversion is good and have than the better image quality of the image that produces without charge control agent.
Disperse test
Resin among the example 3F is assessed its pigment dispersiveness and color depth.
Material:
Select the prescription of two kinds of color depths.A kind of is (PB) 15:3 (PB) of 10% phthalocyanine blue (phtalo blue) in the polystyrene support resin, a kind of interior conventional green (custom green) of vector resin that is based on ABS (Acrylonitrile ButadieneStyrene, acrylonitrile-butadiene-styrene (ABS)) in addition.This routine is green to be included organic and mixture inorganic pigment, and content approximately is 18%.For example Zinic stearas and Zinic stearas use with the combined dispersant of ethene distearyl acid amides the control sample with typical dispersion agent.And sample is with the disperse additive of usage example 3F.
Mix:
18 mm dias that are blended in Leistritz company rotate synchronously in the twin screw extruder and carry out.
Test:
Disperse test to carry out, and the pressure of setting up is to represent with crust/gram (bar/gram) pigment with filtering test.This is the quantitative test to dispersiveness, and lower value representation is better dispersed.
Table 17 shows prescription and the test result that is used to test.
Table 17
| The prescription sequence number | Pigment | Vector resin | Disperse additive | Filter test value crust/ |
| A | ||||
| 10％PB 15:3 | Polystyrene | Zinic stearas | 8.5 | |
| B | 10％PB 15:3 | Polystyrene | Example 3F | 4.5 |
| C | 18% mixes | ABS | EBS and Zinic stearas | 0.82 |
| D | 18% mixes | ABS | Example 3F | 0.55 |
PB=phthalocyanine blue (Phtalo Blue)
ABS=acrylonitrile-butadiene-styrene (ABS) (Acrylonitrile Butadiene Styrene)
EBS=ethene distearyl acid amides (Ethylene Bistearamide)
Compare with the dispersion agent Zinic stearas on the market, the mixture of EBS and Zinic stearas has shown good result.The result has shown the color development preferably that continues in two kinds of different polymer systems.
Disclosed protein is useful in the present invention in WO 04/077,169.This useful in the present invention protein can obtain from animal or plant resources, for example soybean protein, zein, collagen, casein, endosperm, fish-protein and analogue.Protein ingredient scope in the toning agent all is useful from 0wt% to 20wt%.Preferred protein ingredient content is the scope of 0.1wt% to 10wt%.Protein provides the improvement to deinking character.
Though the present invention in this announcement comprises preferred embodiment, also have many additional embodiments.Do not plan to mention deriving of all possible equivalents or invention at this.The reader is to be understood that the term of using is descriptive herein, rather than restrictive, and can make various changes and do not break away from the spirit and scope of the present invention.
Claims (19)
1. a thermoplasticity toning agent synthetics is characterized in that, comprises the mixture of following material:
A, the amorphous thermoplastic polymer of from following, selecting:
(1) carboxyl or hydroxyl-functional polyester;
(2) polyester ether;
(3) urethane;
Wherein, described polymkeric substance is to obtain from least one monomer based on biology, and described polymkeric substance has 50 ℃ to 80 ℃ T
g
B, be dispersed in the pigment in the described amorphous thermoplastic polymer; And wherein, described toning agent comprises that mean particle size is less than 30 microns particle.
2. thermoplasticity toning agent synthetics according to claim 1 is characterized in that, comprises the carboxyl-functional polyester with the pigment-dispersing that has improved.
3. thermoplasticity toning agent synthetics according to claim 1 is characterized in that described mixture further comprises:
C, be dispersed in the protein particulate in the described toning agent.
4. toning agent according to claim 1 is characterized in that, described carboxyl-functional polyester obtains from dihydroxyl hexitol, the first diacid group and/or the second diacid group, also optionally adds an acid.
5. toning agent according to claim 4 is characterized in that, described dihydroxyl hexitol comprises the Isosorbide group, and described first diacid is a 1,4 cyclohexanedicarboxylic acid, and described second diacid is the long chain diacid that has 8 or more carbon atom in the chain.
6. toning agent according to claim 1 is characterized in that, described toning agent comprises the biomass of 5wt% at least.
7. toning agent according to claim 6 is characterized in that, the particulate mean particle size that described toning agent comprises is less than 20 microns.
8. toning agent according to claim 1 is characterized in that, comprising:
D, from the following vehicle of selecting that comprises charge control agent, flow control agent, lubricant, anticaking agent and composition thereof.
9. toning agent according to claim 1 is characterized in that, described toning agent has the negative or positive triboelectric charge of 10 to 40 microcoulomb/grams.
10. toning agent according to claim 9 is characterized in that, described toning agent has the negative friction electric charge of 10 to 20 microcoulomb/grams.
11. toning agent according to claim 1 is characterized in that, described toning agent has the negative friction electric charge.
12. toning agent according to claim 1 is characterized in that, described thermoplastic resin comprises the polystyrene CALCIUM ACRYLATE that is mixed with the polymkeric substance of selecting in the claim 1.
13. toning agent according to claim 1 is characterized in that, described thermoplastic resin is a polyester.
15. photographic developer according to claim 14 is characterized in that, described photographic developer comprises magnetic substance.
16. an image comprises substrate and is coated in suprabasil toning agent according to claim 1.
17. a toning agent is characterized in that, comprising:
(1) thermoplastic polyester comprises the reaction product of following material:
A, dihydroxyl hexitol;
B, dimer diol and/or dimer diacid;
C, diacid, diester or diacid chloride; With
D, optional catalyzer; With
(2) pigment.
18. a photographic developer is characterized in that, comprising:
(1) thermoplastic polyester comprises the reaction product of following material:
A, dihydroxyl hexitol;
B, dimer diol and/or dimer diacid;
C, diacid, diester or diacid chloride; With
D, optional catalyzer;
(2) pigment; With
(3) carrier.
19. photographic developer according to claim 18 is characterized in that photographic developer comprises magnetic substance.
20. disclosed all are novel and non-obvious material, method and use.
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US66342205P | 2005-03-18 | 2005-03-18 | |
| US60/663,422 | 2005-03-18 | ||
| US75875706P | 2006-01-13 | 2006-01-13 | |
| US60/758,757 | 2006-01-13 | ||
| PCT/US2006/010136 WO2006102280A1 (en) | 2005-03-18 | 2006-03-20 | Toner |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101189276A true CN101189276A (en) | 2008-05-28 |
| CN101189276B CN101189276B (en) | 2012-08-29 |
Family
ID=39481088
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800144389A Pending CN101595158A (en) | 2005-03-18 | 2006-03-20 | Resin, low temperature formulations and by the coating of its acquisition |
| CN2006800137737A Expired - Fee Related CN101189276B (en) | 2005-03-18 | 2006-03-20 | Toner |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2006800144389A Pending CN101595158A (en) | 2005-03-18 | 2006-03-20 | Resin, low temperature formulations and by the coating of its acquisition |
Country Status (1)
| Country | Link |
|---|---|
| CN (2) | CN101595158A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8084176B2 (en) | 2008-06-02 | 2011-12-27 | Ricoh Company, Ltd. | Toner, developer, and image forming method |
| CN104252104A (en) * | 2013-06-27 | 2014-12-31 | 施乐公司 | Toner having improved photographic fixing performance |
| CN105278269A (en) * | 2014-06-11 | 2016-01-27 | 卡西欧计算机株式会社 | Electrophotographic toner using bioplastic and production method thereof |
| CN108603016A (en) * | 2016-02-03 | 2018-09-28 | 大和制罐株式会社 | Polyester and resin composition |
| CN109996829A (en) * | 2016-11-30 | 2019-07-09 | 株式会社可乐丽 | Polyester, its manufacturing method and the molded product formed by it |
| CN115926132A (en) * | 2022-03-09 | 2023-04-07 | 苏州恒昇昌进出口有限公司 | Polyester material and application thereof to sound absorption board |
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| EP2694603B1 (en) | 2011-04-05 | 2016-11-02 | Allnex Belgium, S.A. | Radiation curable compositions |
| EP2644634A1 (en) * | 2012-03-30 | 2013-10-02 | Cytec Surface Specialties, S.A. | Radiation curable (meth)acrylated compounds |
| CN109563245B (en) * | 2016-05-30 | 2021-02-26 | 株式会社三养社 | Polyester resin comprising biomass-derived monomer, method for preparing same, and powder coating composition comprising same |
| CN107254035A (en) * | 2017-04-20 | 2017-10-17 | 浙江传化天松新材料有限公司 | A kind of polyester resin for powder coating of β hydroxyalkyl amides solidification water-tolerant and preparation method thereof |
| CN107266666A (en) * | 2017-04-20 | 2017-10-20 | 浙江传化天松新材料有限公司 | A kind of also to bloom low temperature hydroxyalkyl amide cured powder paint polyester resin and preparation method thereof |
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| DE3115071A1 (en) * | 1981-04-14 | 1982-10-28 | Bayer Ag, 5090 Leverkusen | METHOD FOR PRODUCING POLYESTERS USING MANNITE OR SORBITE DERIVATIVES, MIXTURES OF POLYESTERS AND THESE MANNITE OR SORBITE DERIVATIVES AND THEIR USE FOR THE PRODUCTION OF AQUEOUS BURNING VARNISHES |
| US5179143A (en) * | 1988-07-26 | 1993-01-12 | Bayer Aktiengesellschaft | Process for the preparation of compression molded materials |
| US5102762A (en) * | 1989-11-13 | 1992-04-07 | Eastman Kodak Company | Polyesters and toners made therewith which absorb ultraviolet light |
| US5306590A (en) * | 1991-12-23 | 1994-04-26 | Xerox Corporation | High solids liquid developer containing carboxyl terminated polyester toner resin |
| US6063464A (en) * | 1998-04-23 | 2000-05-16 | Hna Holdings, Inc. | Isosorbide containing polyesters and methods for making same |
| GB0207345D0 (en) * | 2002-03-28 | 2002-05-08 | Unichema Chemie Bv | Polyurethane |
| JP4532469B2 (en) * | 2003-02-27 | 2010-08-25 | バテル・メモリアル・インスティテュート | Easy deinking toner particles |
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2006
- 2006-03-20 CN CNA2006800144389A patent/CN101595158A/en active Pending
- 2006-03-20 CN CN2006800137737A patent/CN101189276B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8084176B2 (en) | 2008-06-02 | 2011-12-27 | Ricoh Company, Ltd. | Toner, developer, and image forming method |
| CN101598911B (en) * | 2008-06-02 | 2012-12-05 | 株式会社理光 | Toner, developer, and image forming method |
| CN104252104A (en) * | 2013-06-27 | 2014-12-31 | 施乐公司 | Toner having improved photographic fixing performance |
| CN105278269A (en) * | 2014-06-11 | 2016-01-27 | 卡西欧计算机株式会社 | Electrophotographic toner using bioplastic and production method thereof |
| CN108603016A (en) * | 2016-02-03 | 2018-09-28 | 大和制罐株式会社 | Polyester and resin composition |
| CN108603016B (en) * | 2016-02-03 | 2021-02-12 | 大和制罐株式会社 | Polyester resin composition |
| CN109996829A (en) * | 2016-11-30 | 2019-07-09 | 株式会社可乐丽 | Polyester, its manufacturing method and the molded product formed by it |
| CN115926132A (en) * | 2022-03-09 | 2023-04-07 | 苏州恒昇昌进出口有限公司 | Polyester material and application thereof to sound absorption board |
| CN115926132B (en) * | 2022-03-09 | 2024-03-22 | 苏州恒昇昌进出口有限公司 | Polyester material and application thereof in acoustic panel |
Also Published As
| Publication number | Publication date |
|---|---|
| CN101189276B (en) | 2012-08-29 |
| CN101595158A (en) | 2009-12-02 |
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